CN102574758A - Method for improving the color number of trimethylolpropane - Google Patents
Method for improving the color number of trimethylolpropane Download PDFInfo
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- CN102574758A CN102574758A CN2010800348772A CN201080034877A CN102574758A CN 102574758 A CN102574758 A CN 102574758A CN 2010800348772 A CN2010800348772 A CN 2010800348772A CN 201080034877 A CN201080034877 A CN 201080034877A CN 102574758 A CN102574758 A CN 102574758A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/94—Use of additives, e.g. for stabilisation
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention relates to a method for producing trimethylolpropane having a low color number by processing a raw reaction solution obtained according to the inorganic Cannizarro process while adhering to precisely defined pH values.
Description
The present invention relates to a kind of being used for through under the pH value that accurately limits at a kind of rough reaction soln that obtains through inorganic Connizzaro (Cannizzaro) method being carried out the method that separation and purification (work-up) prepares the TriMethylolPropane(TMP) with low chromatic number.
TriMethylolPropane(TMP) (being called as TMP hereinafter) is widely used in production polyester, polyurethanes, polyethers, foam of polymers class, softening agent class, Synolac class, protection paint class, slipping agent class, the final treatment agent class of textiles and elastomerics class in industry.In addition, it has replaced glycerine in some industrial application.
On a technical scale; TMP for example prepares through the Connizzaro method; This Connizzaro method comprises: in first step, make butyraldehyde and formaldehyde carry out aldol reaction, and in second step, between the aldol reaction product of first step and formaldehyde, carry out cross Connizzaro reaction.When a kind of mineral alkali of this method through consumption stoichiometric calculation value, like sodium hydroxide or calcium hydroxide, when carrying out, it also is called as a kind of inorganic Connizzaro method.The dihydroxymethyl butyraldehyde that in first step, forms as the aldol reaction product generates corresponding formate with excessive formaldehyde generation disproportionation reaction with formation TMP and according to used alkali in second step, for example sodium formiate or calcium formiate.
Commercially available TMP grade has painted usually, and it is that existence by impurity causes.Yet in some applications, this is painted to have disturbed the production of for example transparent especially polyester or special surface-coated raw material.Multiple different separation purification method has been described in document, allegedly can have been realized the improvement of the chromatic number of TMP through these methods.
The separation and purification of the reaction mixture (as obtaining through the Connizzaro method) that contains TMP comprised generally remaining residual alkali in this reaction mixture is neutralized.Typically be enrichment step and to inorganic by product and the organically removal of secondary products after this neutralization, wherein the latter goes out through fractionation by distillation often.
US 3,097, and 245 have described the method that a kind of production has the TMP of the APHA chromatic number in 50 to 200 scopes.This chromatic number is to realize through observing in cannizzaro reaction about the special reaction conditions of the concentration of temperature, reaction times, pH and initial compounds.In addition, after this reaction, with the resulting rough TMP solution of a kind of ion exchange resin treatment.
US 5,603, and 835 have disclosed and a kind ofly produce the method that has less than the TMP of 100 APHA chromatic number through with a kind of ether or a kind of ester the thick solution of TMP being extracted aftertreatment.
All there is following shortcoming in above-mentioned two kinds of methods of improving the chromatic number of TMP, that is: owing to must accurately observe specific conditions, and they need make spent ion exchange resin or introduce at least a solvent and make complicated technically in addition.
SU-A 125552 has described a kind of being used for carried out the hydrogenization of purifying by the TMP of Connizzaro method preparation.After distillation, having provided the content that has through the hydrogenization of nickel, zinc, molybdenum or copper catalyst is about 98% TMP.Stated that the TMP that is obtained is colourless, but do not reported chromatic number.Yet, found that in practice the chromatic number that obtains through this method all is not satisfied for many purposes.
Improve a kind of other method of TMP chromatic number describes in patented claim DE 19963442A through hydrogenization to some extent.Here, after TMP is produced, it is carried out purifying and preferably under hydrogen pressure, uses heterogeneous catalyst to handle subsequently through distillation.Chromatic number through hydrogenation obtains can be through further improving in preceding repeatedly distillation.
Yet, be used to improve the shortcoming that all method for hydrogenation of chromatic number have and be: the high expense of device and because the result of catalyst abrasion reduces the quality of the TMP of gained.The cost of catalyzer has also reduced economical efficiency.
DE 10029055A has described the method that is used for a kind of TMP of improvement chromatic number; Wherein, Make carry out prepurification through distillation and have preferred＞95% purity TMP preferably under 160 ℃ to 240 ℃ temperature through heat-treated; And subsequently this TMP is carried out purifying once more, preferably carry out through distillation.The secondary component that this heat treatment step will be given color is transformed into more high boiling, nonvolatile relatively component.Yet the shortcoming of this method is: in order to remove the TMP that these more high boiling secondary components and acquisition have low chromatic number, must follow another purification step (for example distillation) after this thermal treatment, or this purification step must be united with thermal treatment.
DE1493048B has described through rough TMP being carried out thin-film evaporator of distillatory and has carried out separation and purification.At first will this rough TMP neutralize, carry out then centrifugal and pass a flash evaporator and obtain the pH of about 4-8, preferred 5-6 subsequently, this be before final purifying.The TMP chromatic number that is obtained can reach 0APHA.The shortcoming of this method is must be two local adding acid in this method.This acid is used to neutralization, and does not point out the setting of pH.DE 10164264A explains that a kind of preparation has the method for the TMP of low APHA number; Wherein in the presence of mineral alkali, n-butyraldehyde and formaldehyde are reacted the reaction mixture that contains TMP to provide; From these reaction mixtures, remove water and inorganic salt at least in part; And the rough TMP that is obtained is removed high boiler and low boil-off dose at least in part, these high boilers and low boil-off dose through distillation divide by from become one or more low boil-off dose of cuts, one or more mainly contain middle runnings and one or more high boilers and/or low boil-off dose of cut of TMP.
The instance of DE 10164264A is set to pH 6 through formic acid with this reaction mixture after being illustrated in condensation reaction, but less than this neutralization not being discussed and not relating to chromatic number.Subsequently this reaction mixture is concentrated, filter out calcium formiate, this mixture is further concentrated, and through a thin-film evaporator the rough TMP mixture that is obtained is distilled then.The content that has from the overhead product of thin-film evaporator be 94.9% and the APHA chromatic number be 148, and after further distilation steps, make purity be 99.4% or 99.1% and the APHA chromatic number be 13 or 8.In comparison example, the purity of acquisition be 99.3% and the APHA chromatic number be 22.Although the TMP that this method provides has a good chromatic number, it has following shortcoming,, in distillation, has adopted 48 high reflux ratio in order to realize this chromatic number that is.
Therefore the target that still exists is, be provided for preparing have low chromatic number TMP's and overcome a kind of effective ways of these shortcomings of prior art.
We have been found that a kind of method that is used to prepare the TMP with low chromatic number now; The reaction of this method through butyraldehyde and formaldehyde in the presence of a kind of mineral alkali is with the reaction mixture that provides a kind of TMP of containing and subsequently this reaction mixture that contains TMP is carried out separation and purification; The method is characterized in that the separation and purification to the reaction mixture that contains TMP comprises that the temperature based on 50 ℃ is arranged on from 4.50 to 5.90 value with this pH that contains the reaction mixture of TMP, wherein the setting of this pH preferably uses a kind of organic carboxyl acid to carry out.
Scope of the present invention comprise above in general sense also or the component of in preferred range, pointing out, value scope and processing parameter hope to some extent and possible combination.
The mol ratio of formaldehyde and butyraldehyde is for example from 2.5 to 6.0, preferably from 3.0 to 5.0, especially preferably from 3.0 to 4.0 and very especially preferably from 3.1 to 3.5 in this reaction.
Be for example from 0.8 to 2.5, preferably from 1.0 to 2.0, especially preferably from 1.0 to 1.4 and very especially preferably from 1.05 to 1.2 from the mol ratio of the alkali equivalent of mineral alkali and butyraldehyde in this reaction.
As mineral alkali, give preferential oxyhydroxide or the carbonate that is to use basic metal or earth alkali metal, particularly preferably be sodium hydroxide and calcium hydroxide, wherein calcium hydroxide is even is preferred.When using calcium hydroxide, this can for example be used as the purity that has for greater than 80%, the product of preferred 90%, preferred especially 95% technical grade.
Therefore the mol ratio of calcium hydroxide and butyraldehyde can be for example from 0.4 to 1.25, preferably from 0.5 to 1.0, especially preferably from 0.5 to 0.7 and very especially preferably from 0.525 to 0.6.
Formaldehyde preferably is used as the aqueous solution, and the content that has is by weight from 10% to 50%.In a preferred variant, used the content that has to be from 25% to 40% formaldehyde by weight.Can other water be joined in this reaction mixture, this has improved the selectivity of this reaction but because more substantial water has also increased the cost in the separation and purification process.
In addition, in this reaction, can add at least a compound that can avoid or suppress the formose reaction at least.The compound that is fit to is known for the person of ordinary skill of the art and for example is described in US 2,186,272, among US 2,329,515, EP 510375A, DE A 4123062 and the DE A 4126730.They comprise: the metal-salt of copper, iron, manganese, chromium, nickel, cobalt, silver, platinum, lead, molybdenum, tungsten, bismuth, vanadium, zirconium, titanium, niobium, hafnium for example, can be randomly make up with bubbling through air or oxygen or boron cpd.Give preferably molysite, like the vitriol of iron (II) and its hydrate and also have the vitriol of iron (III) and its hydrate.The value of employed these compounds can be based on this reaction mixture total amount value for example from 50 to 1000ppm.
In order to carry out this reaction, but give preferably at first in a reaction vessel, to insert at least a portion of formaldehyde and mineral alkali and add the formaldehyde of butyraldehyde and optional part through from 3 to 180 minutes, preferred 15 to 120 minutes, preferred from 20 to 60 minutes especially time period.
Temperature in this reaction can be, for example, and from 20 ℃ to 90 ℃, preferably from 20 ℃ to 60 ℃.
In a preferred variant, in the process that adds butyraldehyde, allow this temperature to raise with a kind of controlled way, for example substantial linear ground is from 20 ℃ to 60 ℃.
After this addition is accomplished, under final temperature, further stirring of this mixture continued for example from 5 to 180 minutes, preferably from 30 to 90 minutes.
In another preferred operator scheme, carry out this reaction continuously, for example a pipeline reactor, a series of container, or plate-type heat exchanger in.
The pH that the reaction mixture that contains TMP that after this reaction, is obtained typically has is in from 9.0 to 11.0 scope.
PH based on 50 ℃ the reaction mixture that contains TMP that temperature obtained is set to from 4.50 to 5.90, preferably from 4.50 to 5.60 and especially preferably from 5.00 to 5.60 then; And very especially preferably from 5.25 to 5.45, wherein adjustment is preferred uses a kind of organic carboxyl acid to carry out.
The organic carboxyl acid that is fit to comprises: monocarboxylic acid, like formic acid, acetate and n-butyric acid; Di-carboxylic acid like oxalic acid, propanedioic acid and toxilic acid, and also has tribasic carboxylic acid, like Hydrocerol A.Preferred organic carboxyl acid is a monocarboxylic acid, and wherein formic acid is preferred very especially.
Unexpectedly be that the chromatic number of this TMP can be provided with through the pH in separation and purification process subsequently by a kind of simple mode and be affected.What take place then is that pH in the mentioned scope is low more, and it is more little that its chromatic number typically becomes.
Yet the formation meeting of secondary reaction such as TMP formate takes place when temperature and the variation of the residence time in along with further separation and purification process in these low pH values, has finally reduced the output of TMP.In addition, a low excessively pH has caused the decomposition of residual formaldehyde among the rough TMP, and therefore causes in this first distillation, bubbling, and this has hindered the stable operation of this equipment.
For those of ordinary skill in the art, being easy to is that neutral pH is confirmed, can realize through a preliminary experiment that changes along with the parameter of selecting to the reaction of carrying out with a high yield in the next excellent chromatic number of this pH.
Further separation and purification after the setting of this pH can be undertaken by a kind of known mode own.This separation and purification process can be carried out in batches or continuously, and the further separation and purification process of wherein a kind of successive is preferred.
In a preferred embodiment of method of the present invention, further separation and purification process basis the present invention includes following steps at least after the setting of this pH:
A) contain reaction mixture TMP, adjusted the water of removing part and formaldehyde randomly from this,
B) contain from this and isolate calcium formiate reaction mixture TMP, adjusted so that provide the crude solution of a kind of TMP of containing,
C), this isolates multiple high boiler (high boiler) from containing the crude solution of TMP so that provide a kind of rough TMP,
D) the rough TMP that obtains according to step c) is distilled so that provide the TMP with low chromatic number.
In a preferred embodiment; The reaction of butyraldehyde and formaldehyde provides after the reaction mixture of a kind of TMP of containing and does not carry out step a) in advance to d in the presence of a kind of mineral alkali) one of, based on 50 ℃ temperature this contain TMP reaction mixture pH thereby be set to from 4.50 to 5.90 value.
In another preferred embodiment, the further separation and purification process after the setting of this pH arrives d according to the step a) that the present invention includes by following statement order):
Step a) is preferably through for example carrying out with a kind of distillation of pattern on different stress levels of multistage operations.Outside dewatering, also removed excessive formaldehyde usually at least in part at this.In removing the process of water, inorganic formate can precipitate, particularly at calcium hydroxide as in the alkali, and these are isolated in step b).
Step b) can preferably be carried out through filtration or centrifugation for example through filtering, depositing and decantate or centrifugation.
Temperature in this separation can be, for example, and from 20 ℃ to 90 ℃, preferably from 50 ℃ to 90 ℃.
Step a) and b) can randomly repeat one or many.
Step c) is preferably carried out through distillation.In a preferred embodiment, make the residence time of a weak point become the possible device that is fit to through thin-film evaporator or short-path evaporator or other and carry out this distillation.In step c), from the rough TMP solution that obtains according to step b), isolate high boiler, wherein for purposes of the present invention, high boiler is the compound that boiling does not perhaps have appreciable vapor pressure under the temperature higher than TMP.The instance of high boiler is the formalin of diTMP and bisTMP and also has higher oligopolymer and the formalin of TMP.
The purity that has is for typically obtaining in step c) greater than 90% rough TMP by weight.
In step d), the rough TMP that obtains according to step c) carries out purifying further through distillation.In a preferred embodiment, this can receive at first isolated influence of hanging down boil-off dose from this TMP in first post.Under this background, low boil-off dose is to have the compound lower than TMP boiling point, for example, and 2-methylol-1-butanols, 1-methoxyl group-2,2-two (methylol) butane and 1-[(methoxyl group) methoxyl group]-2,2-two (methylol) butane.TMP be obtain in the bottom of this post and in another post, distill subsequently at cat head.Step d) can also use hot link coupled post to carry out in an independent distilation steps.Known surrogate is that the side that has or do not have separation device (for example, a partition wall) is divided pillar, can be used as effluent from this pure TMP of these separation devices and takes out.
In an alternate embodiment, step c) and d) can in a distillation, carry out simultaneously, wherein these devices of step c) explanation can use with same mode.
Having low chromatic number and highly purified TMP obtains with the mode of explaining according to the present invention.
Instance
General introduction:
Use is measured APHA chromatic number (according to the color classification of platinum-cobalt colourity, with reference to DIN ISO 6271) by Lico 300 photometers of Dr.Lange.For this purpose, will be placed on from the TMP of 4g to 5g in each case the circular cuvette of a 11mm, this circle cuvette makes this TMP in 100 ℃ of fusings and measurement through the sillicon rubber blocking sealing.Each sample is carried out twice measurement and to these numerical value averagings.
Instance 1:
PH is provided with the influence to the chromatic number of removing the raw product behind the high boiler
In batches, water is to 3.15 molar equivalents the diluting and at room temperature carry out blending with the calcium hydroxide of 0.56 mole of equivalent of formaldehyde of 32% concentration by weight.Allow the butyraldehyde of 1.00 molar equivalents to enter into this container, generated the mixture that is warming up to 50 ℃ through for some time of 50 minutes.The value of butyraldehyde is based on by weight 10% of total mass, and the final concentration of TriMethylolPropane(TMP) is by weight from 15% to 15.3%.After this reaction, this mixture was mixed another 40 minutes at 50 ℃, and this pH is arranged on these values that following form middle finger goes out through formic acid.Subsequently this reaction mixture is by weight from 30% to 33% at the content that under 50 ℃ to 80 ℃ temperature and from 130 to 260 millibars, is concentrated to residual water continuously in three grades of vaporizers.Then sedimentary calcium formiate is being separated from 75 ℃ to 80 ℃ and down the content of this residuary water is being reduced to by weight 1.5% from 80 to 100 millibars and 100 ℃.Isolate these precipitated solid, mainly be calcium formiate through a decanting vessel, and 10 millibars and from 140 ℃ to 150 ℃ down this rough TMP freed remaining low boil-off dose.Freed low boil-off dose rough TMP cat head in the short-path evaporator at 3 millibars and under 140 ℃, distill from 130 ℃, be evaporated up to 60%.In three parallel thin-film evaporators (TFE), under the temperature of 5 to 10 millibars and 170 ℃, will further concentrate from the product of the bottom of this short-path evaporator at the top; So that provide a kind of bottoms, this bottoms contains by weight the TMP less than 10% remnants.
These rough distillments are made up and in one first post, under the top pressure of the head temperature of 230 ℃ bottom temp and 154 ℃ and 30 millibars, separate and deviate to hang down boil-off dose.In another post, under the top pressure of the head temperature of 220 ℃ bottom temp and 136 ℃ and 12 millibars, will distill, and have TMP content by weight＞99% then from the bottoms of these posts.
Rough TMP sample and the finished product after-fractionating post after of taking-up after thin-film evaporator, and confirm its APHA chromatic number.
These instances have shown even through having in low boil-off dose the removal that only thin-film evaporator of a separation phase carries out, under a lower pH, have obtained a raw product of low color apparently.APHA chromatic number after this TMP distills the last time before packing has been considered the residence time and definite.The scope of the purity that has of this TMP is by weight from 99.4% to 99.8% in all cases.
These tests have shown that on this pH even very little minimizing has just caused the remarkable improvement of chromatic number.
Claims (5)
1. method that is used to prepare TMP; The reaction of this method through butyraldehyde and formaldehyde in the presence of a kind of mineral alkali is with the reaction mixture that provides a kind of TMP of containing and subsequently this reaction mixture that contains TMP is carried out separation and purification, it is characterized in that this separation and purification process comprises that the temperature based on 50 ℃ is arranged on from 5.25 to 5.45 value through formic acid with this pH that contains the reaction mixture of TMP.
2. according to claim 1 or claim 2 method is characterized in that the oxyhydroxide of basic metal or earth alkali metal or carbonate as mineral alkali.
3. like each described method in the claim 1 to 3, it is characterized in that this separation and purification process further comprises following at least these steps:
A) contain reaction mixture TMP, adjusted from this and remove water and formaldehyde randomly,
B) contain from this and isolate solid ingredient reaction mixture TMP, adjusted so that provide the crude solution of a kind of TMP of containing,
C), this isolates multiple high boiler from containing the crude solution of TMP so that provide a kind of rough TMP,
D) the rough TMP that obtains according to step c) is distilled so that provide the TMP with low chromatic number.
4. method as claimed in claim 3 is characterized in that step a) and b) repeat at least once.
5. like claim 3 or 4 described methods, it is characterized in that step c) and d) carry out simultaneously.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09167480.4A EP2281794B1 (en) | 2009-08-07 | 2009-08-07 | Method for improving the number of colours of trimethylolpropane |
| EP09167480.4 | 2009-08-07 | ||
| PCT/EP2010/061459 WO2011015644A2 (en) | 2009-08-07 | 2010-08-06 | Method for improving the color number of trimethylolpropane |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610134172.7A Division CN105732314A (en) | 2009-08-07 | 2010-08-06 | Method for improving the number of colours of trimethylolpropane |
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| Publication Number | Publication Date |
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| CN102574758A true CN102574758A (en) | 2012-07-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610134172.7A Pending CN105732314A (en) | 2009-08-07 | 2010-08-06 | Method for improving the number of colours of trimethylolpropane |
| CN2010800348772A Pending CN102574758A (en) | 2009-08-07 | 2010-08-06 | Method for improving the color number of trimethylolpropane |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201610134172.7A Pending CN105732314A (en) | 2009-08-07 | 2010-08-06 | Method for improving the number of colours of trimethylolpropane |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US8686197B2 (en) |
| EP (2) | EP2281794B1 (en) |
| JP (1) | JP5531101B2 (en) |
| CN (2) | CN105732314A (en) |
| WO (1) | WO2011015644A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105431402A (en) * | 2013-08-06 | 2016-03-23 | 欧季亚毕夏普有限责任公司 | Improved manufacture of methylolalkanes |
| CN105452206A (en) * | 2013-08-06 | 2016-03-30 | 欧季亚毕夏普有限责任公司 | Manufacture of methylolalkanes with augmented heat transfer and improved temperature control |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE542625C2 (en) * | 2018-09-28 | 2020-06-23 | Perstorp Ab | Process for production of Pentaerythritol with an increased yield of Di-Pentaerythritol |
| CN114181044B (en) * | 2021-12-03 | 2024-05-17 | 宁夏百川科技有限公司 | Preparation method of high-purity ditrimethylolpropane |
| JP7501778B2 (en) | 2022-01-20 | 2024-06-18 | 三菱ケミカル株式会社 | Method for producing polyhydric alcohols |
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| SE322204B (en) | 1964-05-14 | 1970-04-06 | Perstorp Ab | |
| DE3207746A1 (en) * | 1982-03-04 | 1983-09-08 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING TRIMETHYLOL PROPANE |
| DE4113470A1 (en) | 1991-04-25 | 1992-10-29 | Degussa | METHOD FOR PRODUCING CALCIUM FORMIAT |
| DE4123062A1 (en) | 1991-07-12 | 1993-01-14 | Degussa | Calcium formate prepn. with high yield and quality - by reacting calcium hydroxide and methanol, distilling off methanol and crystallising the prod., used as e.g. cement setting accelerator, etc. |
| DE4126730A1 (en) | 1991-08-13 | 1993-02-18 | Degussa | Prepn. of calcium formate from calcium hydroxide and formaldehyde - uses calcium hydroxide with short solubility time, in presence of inhibitor for auto-condensation of formaldehyde |
| US5603835A (en) | 1994-01-19 | 1997-02-18 | Hoechst Celanese Corporation | Trimethylolpropane color improvement |
| JP4284477B2 (en) * | 1998-12-25 | 2009-06-24 | 三菱瓦斯化学株式会社 | Method for producing high-purity trimethylolpropane |
| DE19963442A1 (en) | 1999-12-28 | 2001-07-05 | Basf Ag | Color number improvement of polyhydric alcohols by hydrogenation |
| DE10029055B4 (en) | 2000-06-13 | 2006-06-29 | Basf Ag | Process for improving the color number of polyhydric alcohols by tempering |
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| DE102007013963A1 (en) * | 2007-03-23 | 2008-09-25 | Lanxess Deutschland Gmbh | Process for improving the color number of trimethylolpropane |
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2009
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- 2010-08-06 JP JP2012523346A patent/JP5531101B2/en active Active
- 2010-08-06 US US13/388,199 patent/US8686197B2/en active Active
- 2010-08-06 CN CN201610134172.7A patent/CN105732314A/en active Pending
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| ES481140A1 (en) * | 1979-05-31 | 1980-02-01 | Polialco Sa | Procedure for obtaining trimethyllopropan. (Machine-translation by Google Translate, not legally binding) |
| CN1340492A (en) * | 2000-06-27 | 2002-03-20 | 三菱瓦斯化学株式会社 | Method for preparing polylol |
| CN101591221A (en) * | 2009-06-08 | 2009-12-02 | 无锡百川化工股份有限公司 | A kind of low temperature condensation and condensated liquid carried out pretreated method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105431402A (en) * | 2013-08-06 | 2016-03-23 | 欧季亚毕夏普有限责任公司 | Improved manufacture of methylolalkanes |
| CN105452206A (en) * | 2013-08-06 | 2016-03-30 | 欧季亚毕夏普有限责任公司 | Manufacture of methylolalkanes with augmented heat transfer and improved temperature control |
| CN105452206B (en) * | 2013-08-06 | 2017-12-26 | 欧季亚毕夏普有限责任公司 | Hydroxymethyl alkane is prepared with the temperature control of the heat transfer of enhancing and improvement |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2281794A1 (en) | 2011-02-09 |
| WO2011015644A3 (en) | 2011-04-21 |
| WO2011015644A2 (en) | 2011-02-10 |
| EP2281794B1 (en) | 2015-10-14 |
| JP5531101B2 (en) | 2014-06-25 |
| EP2462096A2 (en) | 2012-06-13 |
| EP2462096B1 (en) | 2014-10-08 |
| US20120178973A1 (en) | 2012-07-12 |
| CN105732314A (en) | 2016-07-06 |
| JP2013501035A (en) | 2013-01-10 |
| US8686197B2 (en) | 2014-04-01 |
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